2) United States Patent Nakamura et al. ($4) METHOD FOR PRODUCING NICKEL SULFIDE AND HYDROMETALLUR METHOD FOR NICKEL OXIDE ORE (71) Applicant: SUMITOMO METAL MINING CO., LID,, Tokyo OP) (72) Inventors: Shinichiro Nakamura, Tokyo (IP); ‘Osamu Nakal, Tokyo UP); Hiroyukl Mitsui, Toiyo (JP); Keisuke Shibayama, Tokyo (IP) 0) SUMITOMO METAL MINING CO, . Tokyo UP) Assignee: (4) Notice: Suibjct to any disclaimer, the teem of this patent is extended of adjusted under 35 USC. 18446) by 0 days. (21) Appl. No. 54,869 (22) PCT Piles: Dee. 1, 2018 (86) PCT No, § 371 (XI), @) Date: Pc 3P20151083794 Aug. 31, 2017 PCT Pub, Nos WO2016/139858 PCT Pub, Date: Sep. 9, 2016 on 6s) Prior Publication Data 1018/0048760.A1 Feb, 15, 2018 G0) Foreign Application Priority Data Mar. $, 2015 GP) 2015-04369 (1) Insc. corg 5311 C22 44 2B 0 (52) U or (2006.01) (2006.01) (2005.01) 228 3/44 (2013.01); COIG S¥IE (GO13.01); C22m 28448 (2013.01); COFP 200861 (2013.01) Field of Classification Search CPC one COIG 53/11; C228 444; C228 2043; CoLP 200461; Co1B 17/901 ‘Se application file for complete search history. 8) 36) References Cited U.S. PATENT DOCUMENTS. 4sa7347 4 seh > 1OV1985 Lasse ot a 72000 Kobayashi... C228 20043, US 10,017,835 B2 Jul. 10, 2018 U 01001783582, (10) Patent No.: (4s) Date of Patent: ZqTLTSS BE 82010. Kina ta S307 B+ 12013. Shibayama 228 230461 747.787 B2* 62014 Kobayashi... €22B 30005 239 SOLGHIS B2* 122014 Matsubara nn C228 2808 20090265910 AL 122005. Kobayashi aonodteoio4 AL 82006 Chamberlain el doowoig7on2 AL 2008 Kina ta 20100018350 AI L2010. Shaya eta DOILOIZ3AI8 Al* 52011 Rocke cng v2 faye 2OIROOTIGSS AL 32013 Kotuyashi a a1aisiar2 AL 62014 Mita et a POREIGN PATENT DOCUMENTS rp 2749660 AL 72014 2 ogaxinso AY Vion @ dooe-rstox AF 2006 ® doloosiaa A 23010 w 2oULIgI9 A R014 Wo wo 2009158682 AL © 122009 cole ve (OTHER PUBLICATIONS Extended Furopean Search Report dated Feb. 1, 2018, sue to EP Patent Application No, 158840249. Tnernaional Seach Repost dae Feb, 16, 2016, sud for PCT sP201s0837%4 * cited by examinee Primary Evaminer — Timothy € Vanoy (74) Attornes, Agent, or Firm Locke Lord LLP 6 Provided is # method for producing nickel sulfide fom acidic sulfuric acid solution containing nickel, which is ‘capable of suppressing particle diameters of nickel sulfide ‘oblained thereby. The present invention is « method for producing nickel sulfide by causing a sulfurzation reaction by blowing a hydrogen sulfide gas into an acidic sulfivie acid solution containing nickel, wherein: nickel sulfide having particle diameters of $-20 jum and serving as sood crystal is added into an acidic sulfuric acd solution having 4 nickel concentration of 05-50 g/L in an amount of 40-50% by mass relative tothe amount of nickel contained in the acidic sulfuric acid solution; and a hydrogen sulfide sis blown into the acid sulfuric acid solution, into which the seed crystals have been added, while setting the amonat of the hydrogen sulfide gas blown into be within the range ff 0.30-085 Nex kg-Ni al RACT 5¢ ims, 2 Drawing SheetsU.S. Patent Tul. 10, 2018 Sheet 1 of 2 US 10,017,835 B2 FIG. 1 LEACHING STEP ~S1 ' LEACHED SLURRY ¥ SOLID-LIQUID SEPARATION STEP |~~S2 ! | LEACHATE LEACH RESIDUE 1 NEUTRALIZATION STEP_[~~S3 | | NEUTRALIZED NEUTRALIZED FINAL LIQUID: SEDIMENT SLURRY — (SULFIDIZATION REACTION STARTING LIQUID) (SEED CRYSTAL) tt SULFIDIZATION STEP [~~ S4 1 NICKEL SULFIDE POOR LIQUID i (FINAL LIQUID) aviU.S. Patent Tul. 10, 2018 Sheet 2 of 2 US 10,017,835 B2 ‘A AMOUNT OF SEED ORYSTA ADDED 40s OR MORE LESS THAN 105, aNunT OF Seco oRYSTAL ADDED 10% OR MORE 15% OR LESS ELAMoUNT oF SEED ORYSTAL ADDED NORE THAN 150 200% OR LESS © pOUNT OF SEED ORYSTAL ADDED ORE THAW 200 003 OR LESS AVERAGE PARTICLE DIAMETER OF NICKEL SULFIDE (12m) 020° 040° 060 080 © 1.00 BLOW QUANTITY OF HYDROGEN SULFIDE (Nm5/kg-Ni) gUS 10,017,835 B2 1 METHOD FOR PRODUCING NICKEL SULFIDE AND HYDROMETALLURGICAL ‘METHOD FOR NICKEL OXIDE ORE TECHNICAL FIELD. “The preseat invention relates to @ method for producing nickel sulfide, and! more particularly to a method for pro- ‘ducing nickel sulfide in which nickel sulfide is obtained by blowing hydrogen sulfide gas into an acidie aqueous soli tion of sulfuric acid containing nickel and cobalt for sul- fidizaion in a sulfidization step in a hydrometllurgical method for nickel oxide ore using a high pressure acid leaching method and a hydromctallurgical method for nickel ‘oxide ofe fo which the method! for producing nickel sulfide is applied. BACKGROUND ART Hitherto, as @ smelting method for nickel, a method ia ‘which a mat having a nickel grade of about 30% by mass is ‘obtained by dry smelting of nickel sulfide ore and electric nickel is then produced by a chlorine leaching-electmlytic winning method. In recent years, a high pressure aeid leaching (HPAL) > method using sulfuric acid has attracted attention as hydrometallungical method for nickel oxide ore. This method does not inelude dry weatment steps such as eedve- tion and drying steps but includes consistent wet steps unlike general conventional smelting methods for nickel oxide ‘res, and it is thos advantageous in terms of energy ad cost Inaddition, there isan advantage that iis possible to obtain a sulfide containing nickel (hereinafter, also refered to as “nickel sulfide”) in which the nickel grade is improved to about 50% by mass. This nickel sulfide is produced as follows, A sulide precipitate is generated by purifying the Jeachate obtained by leaching nickel oxide ore and then blowing hydrogen sulfide gas into the lechate in the sul- fidization step to cause a sulfidzation reaction. The nickel sulfide is recovered by subjecting the slury obtained from the sulfiization reaction toa sedimentation separation treat- ment using a soli-figuidl separation device such as a thick- “The particle diameter of nickel sulfide 1 be precipitated ‘and generated is in an appropriate range, When the particle «diameter is t00 stall, moisture contained in the sulfide powder that is pressed and dred after solid-liguid separation Increases and the powder is cured, for example, during transportation after being pressed. In addition, the entire surface area of the powder inereases, this the porosity increases, the volume increases as compared to powders having a larger particle diameter even of the same weight, ‘and the conveyance cust increases. Meanwhile, when the paricle diameter isto larg, the nicks! concentration ater the sulfiization reaction inereases and the acta Yield oF nickel decreases. lowever, inthe related arts, method for controlling the particle diameter of nickel sulfide 10 be obtained is not ‘established in a method for obtaining nickel sulle from an acidic solution of sulfuric acid containing nickel, and 2 method for stably producing nickel sulfide having a desired particle diameter is demanded. Patent Document I discloses @ method in which a com= plex salt soltion ofan ion of a base metal such as nickel is ‘atomized by using a nebulizer so as to havea certain particle diameter, the complex sat solution of atomized hase metal js brought into contact with of inlodvced into a reducing 2 solution or reducing yas which raets with this base metal t0 instantly reduce the partieulate base metal complex salt 0 4 ‘metal, and the fine metal powder thus obtained i recovered. More specifically, this citation 1 discloses a method for ‘controling the particle diameter ofthe fine metal powder by changing the solution concentration of the metal complex and the diameter of the nozzle mesh which is attached to the ‘nebulizer and contol the diameter ofthe droplet discharged from the nebulizer. However, in the case of applying this nethod to the hydromietallurgieal method for nickel oxide ‘ore, suspended solids contained ia the leachate to be sup- plied to the sulfdization step become clogged in the pores of the ncbulizer and this causes a decrease in the working rate of operation, Patent Document I: Japanese Unexamined Patent Appli= cation, Publication No. 2006-75708 DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention “The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for producing nickel sulfide that can contol the particle diameter of nickel sulfide to be obtained in a method for ‘oblaining nickel sulfide from an acidic solution of sulirie acid containing nickel Means for Solving the Problems The present inventors have conducted intensive investi- gations to solve the problems described above. As a result thus been found out that tis possible to stably obtain nickel sulfide of which the particle diameter is contrlled to be ia f prodetemnined range by sxiding nickel sulfide having aa adjusted particle diameter at « proportion to be in a specific Amount with respect tothe amount of nickel contained in an acidic solution of sulfuric acid and blowing bydrogea sulfide as into the acide solution of sulfuric acid to whieh 9 sood fenystal has boen added in specific low quantity to cause 1 sulfidization reaction, thereby completing. the present invention. In other words, the present invention provides the following, (1) A first aspect ofthe present invention is a method for sradcing niekel sulfide, he method incinding obtaining nickel sulfide by blowing hydrogen sulfide gas into an acidic solution of sulfuric acid containing nickel to cause a su- Tidization reation, ia which nickel sulfide having a particle siameterof from 5 to 20 jm a a seod crystal is added to the acide solution of sulferc acid having a nickel concentration Of from 0.5 w 5. g/L in an amount to be at a proportion of from 40 to 500% by mass with respect 10 an amount of nickel contained in the acidic solution of sulfuric acid and the hydrogen sulfide gas is blown into the acidic solution of sulfuric acid to which the seed erysta is added whose blow quantity is from 0.30 «© 085 Nav hkp-Ni {@) A second aspect ofthe present invention i the method {or producing nickel sulfide according to the firs aspect, ‘whieh a plurality of sulfiization reaction tanks are used and hydrogen sulle gas of the blow quantity is blown atleast ‘nto a first sulfidization reaetion tank for initially easing a salidization reaction, (G) A third aspect of the present invention isthe method or producing nickel sulfide according to the first or second aspect, in which nickel sulfide having a particle diameter of rom $ to 20 jm as the seed erystal is added at a proportionUS 10,017,835 B2 3 ‘of from 100 to 150% by mass with respect to an amount of nickel contained in the acidic solution of sulfuric acid containing nickel (4) A fourth aspect ofthe present invention is the method {or producing aikel sulfide according to any one ofthe frst $ to third aspects, in which the blow quantity of hydrogen sulfide gas is from 0.33 10 0:82 Nm kg-Ni (5) Ath aspect ofthe present invention s the method for producing nickel sulfide according to any one of the fist 10 Tour aspects, in which nickel sulfide obtained by the sulfidization reaction is repeatedly used as nickel sulfide to be added as the seed crystal (6) A sixth aspect of the present invention isthe method {or producing nickel sulfide acconting to any one ofthe fst to ith aspects, in which the acidic solution of sulfuric acid ‘containing nickel is leachate obtained by subjecting nickel foxide ore fo a leaching teatment using sulfuric acid in 3 hydrometallurgical method for niekel oxide ore. (7) A seventh aspect of the present invention is hyeo= ‘metallurgical method forniekel oxide oreo Teach out nickel fom nickel oxide ore by using salfurie acid and to generate sulfide containing nickel from the leschate obtained, the method inchiding 8 sulfidization step of adding nickel sul- fide having a parele diameter of from 5 t 20 ym as a seed ‘eystal toa leachate having a nickel concentration of fom 1055 5.0 gil in an amount to be ata proportion of fom 40 1 500% by mass with respect 10 an amount of nickel ‘contained in the leachate and blowing hydrogen sulfide gas Jno the leachate to which the seed erysal is added whose blow quantity is from 0.30 to 0.85 Nmv'rkg-Ni fo cause & sullidzation reaction, fees of the Invention According tothe present invention, its posible to obi nickel sulfide of which the particle diameter is controlled to be ina predetermined range. BRIBE DESCRIPTION OF THE DRAWING: FIG. 1 is a process chart illustrating the procedure of a hydrometallungical method for aickel oxide ore. TIG. 2 is a graph illustrating the relationship between the ‘average particle diameter of nickel sulfide generated and the blow quantity (added quantity) of hydrogen sulide ans. PREFERRED MODE FOR CARRYING OUT ‘THE INVENTION Hereinafter, specific embodiments of the present inven 50 tion (hereinater refered to as dhe “present embodiments”) I be deseribed in detail Incidentally, the present inven- tion is not limited 10 the following embodiments, and various modifications are possible without changing the gist of the present invention Incidentally, in the present specification, the case of expressing “X to Y" (X and Y are arbitrary numerical values) means “rom X or more t Y or Jess” unless clherwise stated, <<1. Overview>> ‘The method for producing nickel sulfide according to the present embodiment is a method for obtaining nicks! sulfide by blowing hydrogen sulfide gas into an acidie solution of sulfrie cid containing nickel to cause a sulfidization reac- tion, Here, nickel sulfide is sulfide containing nickel, and it also includes a mixed sulfide of nickel and snother metal such as cobalt, o 4 Specifically, in this method fr prucingaickel sulfide, sickel suid having a particle diameter of from So 20 ym asa sex etal is aded 1 the aide solution of sulvic ‘ci contsining nickel sta concentration of from 0.5 to 5.0 {in an amount o be at a proportion of from 40 to 500% bbymasewith respect tothe stout of nickel eontaine in the acidic soltion of slfrie acd. Moreover, hydrogen slide G,S) gas is blow into the acide solution of sre acid to which the seed erystal is added by seting the blow quanti wo from 030'10 08S Navkg-Ni wo cause a sle Hiization reaction AAS Will be described later, this method for producing eke slide canbe appa to the treatment in a sulfiiza- tion step in hydometlurical method for nickel oxide core. At thi time leachate obtained by subjecting the nickel ie oreo the feaching teatment using sulfrc acid ean be eda the acidic solution of sufire acid containing ick. Ineidetally as will be describe Iter, he nealized ial liquid obtained by neuraliing the Isc obtained trough the leching tretmeat wih neutralizer may be used “Theaccie solution of sulfuric acid containing nickel isan aciie agucous solution of sulfric eid having 0 niekel Concentration of from 08 to 5.0 This acide soliton of Sulfuric eid may’ contin, for example, cobalt roa, mane fanese, magnesium, aluminum, chromium, and lad 28 Slements other than aickel. In the method for producing nickel sulfide according to the present embodiment, the Sulidizaton reaction is caused by introducing su an see Soliton of slfrie acid contining nickel asa suliization reaction stating Tigid hereinafter, also sinply referred to fsthe starting lig”) nto a pressure resistant uliztion reaction tank and blowing hydrogen sole gas asa sul- Fidving agent into the reaction teak ‘With regard (0 the aickel concentration ia the acidic solation of sulfuric acid to be the sulidiation reaction Starting Tig, the acta yield of nickel decreases singe the rickel concentration is too low when iis les than 0.5 iL. ‘Meanie, inthe ease ofan ace solution of sulfuric acid having a sickel concentration of more than $0 gil, is required to prepre the acidic solution of sulfuric eek by ting for example, nickel ore ore having high nickel rade a8 raw material, but such an oxide ore having a high Bickel grade is burly available nd iti thus dill fo Stably and efcienly obtain aickel slide Here, in the suliization reaction tank ia which che sulfation weaetion aks place, after the aii solution oF Sulfrie acid ofthe starting igi is ntradiced thers, Iydeogen slide gas supplied from a hydrogen sulfide gas producing Taiity or the ike is Bown ino the pas phase Portion i the rseton tank and the hyerogen sulfide Basin the was pase i solved inthe igi phase, whareby the sulidization reaction proceds "The sulidizationrenetion ank snot particulary Hited but forexample, ts possible to se a multistage continuous stirring sulidiaton reaction faity consisting of phil Stages of sulfidization roction tanks such as for stages Usialy, the sullgivation reaction tank is 2 sealed type reaction tank equipped wih an inlet for inducing the ‘eavtion starting iid, aa out for discharging the shery aie the reation, 2 gas bing port Tor blowing hydrogen Sulfide a, and an exaust gas out for discharging @ prt ofthe gas in the solidization reaction tanks exhatst gas. Specifically, for example, inthe sufdization reaction facil consisting ofthe four stages of suliization ration tanks as desribed above, fit a acide solution of slic cid contsining nickel ofa reaction starting gid i tox dled into the fist suldizaton reeton tak of the iiiUS 10,017,835 B2 5 reaction faak among the reaction tanks which are eontiny- ‘ously provided and also hydrogen sulfide gas is blows into the gas phase portion in the reaction tank through the gas blowing por. Thereafter, when the sulfidization reaction is ‘cause in the fest sulfidization reaction tank fora predeter- mined time, the solution containing the generated nickel sulfide is then transfered into the second. sulfiization reaction tank and hydrogen sulfide gas is appropriately supplied thereto to cause the sulfidization reaction. There- aller, the sufidization reaction sequentially proceeds in the ‘hied sulldization reaction tank and the fourth sulization reaction tank, and nickel sulfide and the poor liquid of the reacted final Tguid are separated from the slurry alter the reaction obtained in the fotith slfidization reaction tank by using solid-liquid separation device sich asa thickener. [a this manner, for example, ina sulfiization action facility ‘consisting of four stages of sulidization reaction tanks in total a reaction for the generation of nickel sulfide based on the Sulfidization reaction takes place mainly in the first sullidization reaction ank and the so-called growth of nickel sulfide thas generated takes place in the subsequent second to fourth sutidization reaction tanks, In this manner, upon generating nickel sulfide from an ‘scidic solution of sulfuric acid containing nickel by 9 sulidization reaction, itis possible to elicently cause the eneration of nickel sulfide and the growth of the nickel sulfide generated to a desired size by using a sulliization reaction facility consisting of a plurality of sulliization reaction tanks. In the method for producing nickel sulfide according 10 the present embodiment, upon causing the sulidization reaction by using the sulidization reaction tank as described above, nickel sulfide adjusted 10 have a predetermined particle diameter as a seed erystal is added tothe sulfidiza- tion reaction starting igi introduced into the reaction tank. In this manner, the seed crystal serves as 4 nucleus for the ‘generation of nickel sulfide to be newly precipitated and enerated by the sulfidization reaction by adding. nickel sulfide having a predetermined particle diameter as the seed ‘ysl, and itis possible to enbanee the setleabibity of fine Aickcl-containing particles present inthe solution by increasing the partite diameter ofthe nickel sulfide particles to be generated, This makes it possible to sulliciealy recover the fine particles as a precipitate of nickel sulfide ‘Specially. in this method for producing nickel sulfide asa seed enystal, nickel sulfide adjusted to have a particle ‘diameter of from § to 20 um is added in an amount to be at a proportion of from 40 t 500% by mass with respect to the amount of nickel contained in the sulidization reaction saring liquid. The method for adjusting the particle diameter of nickel sulfide to be added as a seed enystal is not particularly Timited, and for example, the panicle diameter can be adjusted by performing « classification treatment ata elas- sification point set so that the particle diameters equal 1 oF larger than a predetermined size by using a wet cyclone (also refered to as “liquid cyclone”), a vibrating type serven machine, or the lke. Among. the methods for adjusting the particle diameter, its particularly preferable to uses mtethod to perform a clastifcation treatment using a liquid eyelone. According tothe method using a liquid eyclone, collision or ‘contact between nickel sulfides occurs in the eyclone granu Tation proceeds by this, and it is thus possible to. more cfficiently adjust the particle diameter to be in an appropriate range "As described above, the amount af nickel sulfide added as «4 soed erystal is set fo an amount to be at proportion of 0 o 6 from 40 10 500% by mass with respect to the amount of sick contained in the sulfation reaction starting ig ‘When the amount of nickel sulle added i es than 40% by mass with respect tothe amount of nickel in the sulfation reaction staring liquid, there is a possibilty that nickel sulfide the obtained has a particle diameter of larger than {60 um, Meanshile, when the amount of nickel sulfide added exceeds 500% by mass with respect tothe amount of nickel contained in the starting liquid, ther isa possibilty that the sick! concentration inthe lguid (reacted final lid) after the sulfation eatin is completed is more than 0.25 gi, and the actual yield of nickel decreases TInaditon, it is more preferable tat the amount of nickel sulfide added as a seed crystal is an amount to be at a ‘proportion of from 100 to 150% by mass with respect to the mount of nickel contained in the sulfation reaction starting liquid. In this manner, by repeatedly using nickel sulfide having a particle diameter of from 5 to 20 um as a seed erystal 30 as to have an amount of nickel of from 100 to 150% by mass with respect 10 the amount of nickel contained inthe sulfdization reaction staring liquid and adding hydrogen sulfide gas ina predetermined blow quan- tig; iis possible to more effectively control the particle ameter of nickel sulfide to be obtained to be inthe most preferable parle diameter range, specifically, a particle ameter range of from 10 1 60 yn. In the method for procing nickel sulfide according 0 te present embodiment, as described. above, hydrogen sulfide gas is blown into the sulfidization reaction starting liquid to which the seed erystal is added at a predetermined proportion by adjusting the blow quantity t from 0.30 to O85 Nin keNi ‘When the blow quantity of hydrogen sulfide gas i less than 030 Navkg-Ni, supply of sulfur (S) forthe sulidiza- tiom reaction i insucient so thatthe set yield of nickel decreases. Meanwhile its inelicient thatthe blow quantity of hydrogen sulfide gos exceeds 0.88 Nm'ikg-Ni, sulfur ‘more than the amount of sulfur requited forte sulfiization ‘action i supplied and apart ofthe blown hydrogen sulfide as is wasted In addition, as a method for adding (blowing method) hydrogen sulfide gas, itis possible to add the entire quantity cof hydrogen sulfide zs to be supplied to the fist suliiza- ‘ion reation tank such thatthe addition rate of hydrogen sulfide gas tothe gas phase portion inthe fist sulfidization reaction tank provided inthe first postion is in a range of from 0.33 w O82 NmVkg-Ni, for example, in the ease of ‘using a multistage continous tering reaction facility Alter tatvely, part of hydrogen sulfide pas o be supplied may be adkied 0 the second sulfdization reaction tank while being distributed alte the addition rate of hydrogen sulfide as inthe fit sullidization reaction tank is set be in a range of from 0.33 to 082 Nav /kg-Ni ‘As described above, inthe method for producing nickel sulfide according to the present embostiment, nickel sulfide having a particle diameter of ffom 5 0 20 pm as a soed crystal is added to an acidic solution of sulfric acid con- taining nickel at ¢ concentration of from 0.5 10 5.0 wi. (Gulfidization reaction starting liquid) in an amount to be at proportion of from 40 10 500% by mass with espet to the ‘amount of nickel contained inthe acidic solution of sulfuric acid and hydrogen sulfide gas is blown into the acidic solution of suri ai by setting the blow quantity fom (0.30 to 085 Novkg-Ni to cause the sulfiization reaction. ‘According to such a method, the particle diameter of sick! sulfide to be obtained by the sulfidzation reaction ean be contoled t be ina predetermined range. Specifically, iUS 10,017,835 B2 1 is possible to efficiently produce nickel sulfide of which the average particle diamter is appropriately controlled to be ia a preferable range of about from 10 (0 60 um, ere, the particle diameter of nickel sulfide has an appro- priate range. When the particle diameter of nickel sulfide is too small, the amount of moisture contained in the nickel sulfide powder after the solid-liquid separation treatment Jncreases and the powder is cured. In addition, the entire surface area of the powder inereases, this the porosity Jncreases, the volume increases as compared to powders having a Taryer particle diameter even of the same weight, ‘and the conveyance cost increases. Meanwhile, when the particle diameter is too large, the nickel concentration in the final Tiguid after the sulfidization reaetion increases and the actual Yield of nickel decreases. For these reasons, the particle diameter oF nickel sulle is preferably in a range of rom 10 to 60 um and more preferably in a range of from 1S to 55 ym as an average particle diameter. Incidentally, a the seed crystal to be aided to the acidic solution of sulfuric acid containing nickel ofthe sulliiza- tion rection starting ligui, iis preferable to repeatedly use nickel sulfide obtained by the sulfidization reaction based on the producing method. As described above, in the method or producing nickel sulfide aocording. to the present ‘embosdiment, itis possible to obtain nickel sulfide of which the average particle diameter is controlled to be in 9 prel- ‘erable range of from 10 10 60 jum, itis thus possible to easily ‘adjust the particle diameter to oa 5 to 20 um by classifying the nickel sulfide obtained without almost inereasing the ‘ost, andthe nickel sulfide can be suitably used as @ sed cent. <<2. Application in Hydrometallurgical Method for Nickel Onide Ore>> In the method for producing nickel sulfide according to the present embodiment, an acidic solution of sulfuric acid ‘containing nickel is used as a sulfidization eaetion starting Tiquid and hydrogen sulfide gos is added to this solution t0 ‘cause a sulfdizaion reaction. As the acidic solution of sulfirie acid containing nickel, for example, it is possible to use a leachate obtained by subjecting nickel oxide are to a Jeaching treatment using sulfuric acid, and the leachate is subjected tothe sulfidization reaction to obtain nickel sul- fide. In this manner, the method for producing nickel sulfide ‘acconting to the present embodiment can be applied to 2 hhydrometallurgical method for recovering nickel from nickel oxide ore. Hereinafter, the overview of the hydometallurgial method for nickel oxide ore will be described, ancl specific aspect in which the method for producing nickel sulfide described above is applied to the treatment in the sulfidiza= tion step ia the bydrometallugical method will be thea described. Incidentally, as the hydrometallugical method. fr nickel oxide ore, a hydrometallurgical method using a high pressure acid leaching method (HPAL method) in which leaching is performed at a high temperature and a high pressure is described as an example, 2-1. Respective Steps in lydrometallurgical Method for Nickel Oxide Ore> TIG, 1 is a process eb illustrating an example of the procedure of s hydromeallurgical method for nickel oxide ‘oe, As illustrated in FIG. 1, the hydrometaluraical method or nickel oxide ore includes @ leaching step SI in which sulfuric acid is added to a slurry of nickel ide ore of the raw material and the slur is subjected to a leaching treatment at a high temperature and a high peessure, 2 solid-iquid separation step S2-in which the residue is separated from the leached slurry to obtain a leachate 0 o 8 containing nickel and cobalt, @ neutralization step S3 ‘which the pl ofthe leachate is adjusted sod the lmpurity element inthe leachate is separated as a neutalized sei tment slimy to obtsin « neutralized fine guid, and a Suliizaton step (nickel recovery step) $4 i which hyero- gon slide gor asa sulidiring ageat is added to the eualized al uid to generate nickel sali () Leaching Step In the leaching sep SI, sulfre acid is added to shury (ore sluny) of aickel oxide ore and the mature is sired under condition of a temperature of about from 230°C. 10 270°C. an a presse of bout om 3 MPa to $ Mpa by ‘sing high temperature pressurized reaction tank such as tn atoclve fo-generate leached sluny composed of leach reside and a leachate "Examples of the sickel oxide ore may mainly include so-called laterite oe such as ionite ore and saprolite ore The nickel content in the laterite ore is wsually Irom 03 to 2.5% by weigh, and nickel is contained asa hydroxide ora ‘mognesium silicate mineral. a adition, the content of on js trom 10 to 50% by weight iron is mainly inthe form of 4 valent hydroxide (got), but divalent ion s pay Contained in the magnesim silicate miner In addition. ia theleaching step SI, an oxide ore containing valuable metals sucha nickel, cobalt, manganese, and copper, for example, reserves of manganese nodes on the deep occ Noor ze ‘sed in ation wo such laterite ore. Ta the leaching weatment in this leaching step St, for ccxampl, leaching rections and high temperature them Inyrolysis reactions repeesente by the following Formulas (010 (take place an Teaching out of nickel, cobalt and the like as a sulfite and immobilization of ion sullte leached out as hematite are performed However meso lization of ion ions doesnot proceed to completion, andthe ligaid portion ofthe leached shiny to be obtained umvally conti divalent and talent iron ons in aiton to nick, Cobalt, and the ike. Incidentally, n ths leaching step SI, it js preferable wo adjust the pl of the leachate tobe obtained to fom O.1 to 10 fiom the viewpoint of the fittion property of the leach reside Which is generated in the Solidiguid separation step S2 ofthe next step and contins hematite Teaching Reaction MOWiS0,=>MS0,H,0, ((neidentally, M in Formula () represents Ni, Co, Pe, Zi, Cu, Mg, Cr, Man oF the like) EOIN IHL SO.RP FASO 60 w FeO4H,$0,2980,4H1,0 ‘igh Temperature Thermal Hydrolysis Reaction 2ES0 +1150 440,59 F804) H1L0 6 Fej804)438,059 Fe 0,438.50, © Incidentally, the amount of sulfuric acid added to the autoclave changed with the ore slur’ is not particularly limited, but an excessive amount is used s0 that iron in the fore is leached out. For example, it is from 300 kg to 400 ke per I tonne of ore (2) Solid-Liquid Separation Step In the solid-liguid separation stop S2, the leached slurry generated in the leaching step S1 is washed in multiple Stages to obtain a leachate containing valuable metals sich fs nickel and cobalt and leach residue. ‘In the sold-lguid separation step S2, the leached slury is, subjected to a soliliquid separation treatment using aUS 10,017,835 B2 9 solid-Liquid separation device such a thickener after being mixed with the washing liquid. Specifically first the leached slurzyis diluted with the washing ligud, nd then the leach residue inthe leached shury is concentrated asthe sediment ‘of the thickener. This makes it possible 10 decrease the mount of nickel attached tothe each reside aeconding to the degree of dilution. Incidentally, in the actual operation, its possible to achieve an improvement of the recovery rate ‘of nickel by continvously using thickener having such 2 function in mulsple stages. G) Neutralization Step Jn the neuralization step S3, a neutralizer such es magne- sium oxide o caleium carbonate i add so a8 to adjust the pH to 4 or less while suppressing the oxidation of the Jeachate and neutralized sediment shury containing tiva- ion and neutralized final liquid as a mother liquid for nickel recovery are obtained. Inthe neutralization step S3, a neutralizer suchas calcium ‘carbonate is added to the leachate so that the pHT of the neutralized final liguid to be obtained becomes 4 of less preferably from 3.0 to 3.5, more preferably from 3.1 0 3.3 whl the oxidation ofthe separated leachate is suppressed, and the neutralized final liquid tobe a source of the mother Tiguid for nickel recovery and a neutralized sediment slurry ‘containing trivalent iron a an impurity element are formed. In the neutralization step $3, by subjecting the leachate t0 the neutralization treatment (liquid purification treatment in this manner, the impurities such a trivalent iron fons and sluminum fons remaining inthe solution are removed as @ neutralized sediment 2s Well as the excess acid used in the leaching treatment by the HPAL. method is neutralized to generate a neutralized final Figuid Incidentally, the neutralized final liquid i. solution based ‘on the leachate obtained by subjecting nickel oxide ore of the riw material to the leaching treatment (leaching step SH) using sulfuric acid, and itis the acidic solution of sulfuric acid containing nickel as described above, This neutralized final liquid is a reaction stating Tiquid of the sulfidization reaction in the sulfdization step S4 to be described later, and it has a nickel concentration in a range ‘of about from 05 to 50 gL. In addition, cobalt as a valuable metal other than nickel is contained in this neutralized final liguid, and this neutralized final liquid contains iron, man- anes, magnesium, aluminum, chromium, lead and the like fn trace amounls in some cases even if it i @ solution ‘obtained through the liquid purification treatment {Sulficization Step (Nickel Recovery Step)] Inthe sulidization step $4, the neutralized final liquid of the mother liquid for nickel recovery is used as the sulfidization reaction stating liquid, hydrogen sulfide gas ofa sulidizing ‘agent is blown into the sulfdization reaction starting liquid to cause the sulfiization reaction, and nickel sulfide con- ‘wining a small amount of impurity components and a poor Figuid (guid after sulidization) in which the nickel eon- ‘eniraton is stabilized at a ow level are generated. Inc ‘dentally, ina case in which zine is contained in the neutral ined final liquid, zine can be selectively separated as sulfide prior to the separation of nickel as nickel sulfide. The sullidizaton treatment i the sullidization step Sean be performed by using 2 sulfidization reaction tank oF the Tike, and the sulfidization reaction is caused by blowing hydrogen sulfide gas into the gas phase portion in the sulfidization reaction tank in which the sulidization reaction starting liguid js introduced and dissolving the hydrogen sulfide gas inthe solution. By this sulfidization treatment Aickel contained in the sulfidization reaction stating liquid js immobilized and recovered a8 nickel slide 0 o 10 Incidentally fier the sulidization reaction is completed, the slurry whieh is thus obtained and contains nickel sulfide is charged into a sedimentation separation apparatus such as 4 thickener and subjected to the sedimentation separation {ewatment and only nickel sulfide is separated and recovered {rom the bottom portion of the thickener, Meanwhile, the agucots solution component i recovered as poor guid by Allssing it overflow from the tp portion a the thickener 22-2, Sulfidization Step in Hiydrometallargical Method ere, the method for producing nickel sulfide described hove can be appli to the treatment in the sulidization step 4, namely, th sulidization treatment for generating nickel sulfide from the neutralized fina liquid of te acdc solution of sulfuric acid containing aickel In other words, in the sulfidization step S4 according to the present embadiment, nickel sulfide having a particle ameter of from Sto 20 jum asa seed erystal added to the ‘neutralized final liquid having a nickel eoncenteation of from 5 to 50 gil. (acidic solution of sulfuric acid contsiaing nickel) in an amount to be at 2 proportion of from 40 10 500% by mass with respect to the amount of nickel eon- tained in the neutralized final liquid. Thoreate, hydrogen sulfide gas is blows into the neutralized final liquid by adjusting the blow quantity to from 0.30 t0 0.85 Nm kg-Ni to cause the sulfidization reaction. ‘The specific method for sulfdization treatment is the same asthe method for producing nickel sulfide desribed above, and the detailed description thereof will be thus omitted here, In the present embodiment, nickel sulfide having an adjusted particle diameter as a seed erystal is added 10 the neutralized final Tiquid at a_ predetermined proportion and hydrogen sulfide gas is added tothe neutral- ‘ed final liquid in a predetermined blow quantity to cause the sullidization reaction in this manner. This makes i possible to eliiently and stably obtain nickel sulfide of ‘which the particle diameter is controled to be in a prode- ‘ermined appropriate range, ‘As also illustrated in the process chart of FIG. 1, it is preferable to repeatedly use a part of the nickel sulfide ‘obtained in this sulfidization step S4 in the sulfiization ‘waetion inthe sulfidization step S4 asa seed crystal (artow Rin FIG. 1) As described above, the nickel sulfide obtained through the slfidization step S4 inthe present embodiment tas particle diameter that is controlled to be in an appro- Prite range, specifically, range of about from 10 to 60 jum fasan average panicle diameter Hence, its posible to easily and efficiently obizin nickel sulfide to be added as a seed crystal by repeatedly using the nickel sulfide dus obtained ‘and adjusting the particle diameter of the nickel sulfide thus joblained to be in a range of from $ 10 20 jun through classification treatment or the like. In addition, it is possible to even more effectively control the particle diameter of nickel sulfide tobe obtained tobe in an appropriate range by repeatedly using nickel sulfide in this manner so that the ‘mount of nickel inthe slfidizaton reaction starting liquid is ala proportion of from 40 to 500% by mas. EXAMPLES ervinafter, the present invention willbe described more specifially with reference to Examples, but the present invention isnot limited to the following Examples at al Example A solution of nick! sulfite having a nickel concentration of from 10 0 3.0 asa starting liquid was introduced intoUS 10,017,835 B2 uw 4 fourstage continuous stirring reaction tank, and nickel sulfide having a particle diameter adjusted ta be in a range of fiom 7 to 15 ym as a sead erystal was added to the reaction tank while changing the amount in a range of from 40 to 500% by mass (40% by mass or more and SOOP6 by ‘mass or less) with respect to the amount of nickel contained inthe starting liquid. Incidentally, as presentod in the fl- lowing Table 1. nickel sulfide was added at the respective proportions of 4% by mass or more and les than 100% hy mass, 100% by mass or more and 150% by mass or less. more than 150% by mass and 200% by mans of less, and ‘more than 200% by muss and 500% by mass or less With respect to the amount of nickel inthe starting Kgui. ere, as nickel sulfide ofthe seed crystal, nickel sulfide prepared by concentrating and separating the shury which was obtained by the sulfidization reaction of the solution of nickel sulfate and contained nickel sulfide by using a thick- ‘ener, recovering the nickel sulfide fom the bottom portion ‘of the thickener, and classifying the nickel sulfide by using ‘a Tiguid eyelone to adjust the particle diameter to be in & range of from 7 to 15 jim was repeatedly used, ‘More specifically, in Examples, the seed crystal was audded to the inital reaction tank (fst sulfidization reaction tank) among the four stages of continuous stirring eaction tanks together with the solution of nickel sulfate of the starting liquid aad hydrogen sulfide (HS) gas was supplied 2 such thatthe entre quantity of hydrogen sulfide pas to be ‘pple was supplies! to the ist sllidiation eatin tk ‘ohave a blow quantity added quam) ina range of fom (0.3340 0.82 Nav kg-Ni ora par of the hydrogen slide gas 10 be supplied was also supplied to the second suliization ‘eacton tank while Being dstbute ser the blow uty ot hyrogen slide gs inthe fist suliivation reaction tank twas ac Io e in a range of from 033 to O82 Ne kg-N to {ase the suliization reaction, The slury which was gonrate by such a sulfidization reaction and contaited nickel slide was sent oa thickener dual subjete to a sedimentation separation treatment to Sepaate tho shee nto nickel sulfides poo iid inl Tiguid). The parle diameter of nickel slide sted inthe tyekener aod the nickel concent inthe hud which overflowed the thickener and was a poor Tigi thi ‘were detemined. Incidentally, the particle diameter Bickel slide was measured by using a laser difaetion ype Pattee size dsibution appara. In ation, the nickel Concentration in the liguid overfowed was measured by ‘ing an ICP atomie emission spectrometer. “The respective mearemeat Fsuls are presented in the following Table L-In addition, = graph illstating the relationship between the blow quantity of hydrogen slide 42s andthe average panicle diameter of the nickel slide aencrted is preseited in T1G. 2 TABLE 1 ess than 1008 293 038 ws by mass ot o Amoust of ed consenttion aston mie parle ™ paris fs a a oSUS 10,017,835 B2 13 TABLE L-continved Now dan La io tyme to Ist ts ” Mor tin 200% 13 Ba by mse 2s ie ore io Eg As presente in Table 1 and FIG. 2, it was possible 10 appropriately contol the average particle diameter of nickel sulfide to be precipitated bythe slidization reaction to be in a range of from 15 10 $3 um by adjusting the quantity of hydrogen sulide gas supplid to the solution of nickel sulfate (0 which nickel sifde having an adjusted particle AGameicr a8 a soa crystal was ade, for example, ia an amount of 10% by mass or more and 150% by mass or less with spect othe arionat of nickel contained inthe staring Tigi sch thatthe adition ite of byedrogen sulfide pass the ist sulidization reaction tak was #8 range of fom (036 10 0.82 NinTkg-Ni Tn addition, ina case in whieh the amount of seed eral ached was set o 50% by mass or more and es than 100% by mass and the addon rte of hydrogen slide gas inthe fit suliiation rection tank was adjusted to bo fom (033 10 037 Nmwkg-Ni, it was possible 10 contol the particle diameter of sick slide fo he 3 «range of fom 40 16 60 jm as an average particle diameter although the Particle dimctor tends tobe relatively lrg. Incidentally. Xs found that the nickel concentration inthe fil Liquid aller the slfidzation reaction increased and the acta yield ‘of nickel tendo deerease as compared to a ease in which the amount of nicks sulfide added a the seed crystal was st to 100% by mass o¢ more and 150% by mass o les. Tnaddiion, na case in which th amount of sod erystal sndded was 150% by mass or more and SO% by mass oF less tnt the scion rate of hydrogen sulfide gas a the Aint fullidizatonreation tank was adjusted 0 from 0.38 to 0-74 Nu'kg-Ni, it was possible o consol the purile diameter ‘of nickel sulide to be in a predetermined range at the ‘avenge parle diameter Was from 12-410 32.0 um although the particle diameter endod t be elatively smal. Ineiden- tally t was found tht the sikel concentration inthe Hal Jiguid afer the sulfation reaction was inzeased and the ‘etal yield of nickel tended to decrease compared to 9 ‘ase in which the amount of nickel sulfide added a the seed ‘nyt wa ct 6 100% by mass or more and 150% by exass oF less From the reslls of Examples deseribed above, it was found that is posible to appropriately cont the parle ameter of nickel slide to be obtained toe in prede- termined range by setting the added emovunt of nicks slide having an adjusted particle diameter as the seed ert an amount of 4% by mass or more and 00% by mass or ess ‘with respect the amount of nickel inthe suliization reaction stating liquid and blowing hydrogen sulfide gas nto the sulfdizaGon reaction staring liquid in a blow ‘quantity adjusted to be in 2 range of fom 0:30 to O.8S Nav ikg-Ni to eause tho slfidiation reaction Te was fond that i i possible to contol the particle amt of nickel sulfide to be in « moee appropriate range to keep the nickel conse fal gid low, To more ellestively suppres a decree i 0 o 14 we 0m a no on 2 30 bas ma oe Oa 30 30 on Bs nn te the actual yield of nickel by seting the amount of nickel sulfide added asthe seed crystal to bein a range of 100% by mass or more and 150% by mass or less with respect to the Amount of nickel in the starting liquid among them, Compnaative Example 1 ‘The sulldization revetion was caused by setting the ‘amount oF nickel sulfide added as the sed ery'al to 20% by ‘mas with respect to the amour! of nickel contained in the starting liguid and the blow quantity of hydrogen sulfide gas to be blowin into the first sulfidization reaction tank to 0.20 [Non'/kg-Ni. Incidentally, conditions other than these are the same as in Examples ‘Asa result the average particle diameter of nickel sulfide thus generated was 100 jm oF more, which is too lange Comparative Example 2 ‘The sulfdization reaction was caused by setting the amount of nickel sulfide added as the seed crystal to 600% ‘by mass with espeet othe amount of uiekel contained inthe starting liquid and the blow quantity of hydrogen sulfide gas to be blown into the first sulidization reaction tank to 0.50 ‘Non'ikg-Ni. Incidentally, conditions other than these are the same aia Examples ‘As a result the nickel concentration in the final liquid after the sulfdization eaction was completed was 0.32 pL. ‘which is significantly high and the actual yield of nickel ecreased. In addition, the average particle diameter of nickel sulfide thus obtained was 8 ym, Comparative Exaimple 3 ‘he sulfdization reaction was caused by setting the ‘amount of nickel sulfide added as the see crystal to 20% by ‘mass with respect to the amount of nickel contained in the starting liquid and the blow quantity of hydrogen sulfide gas to be blowin into the first sulfidization reaction tank to 0.37 [Non'/kg-Ni. Incidentally, conditions other than these are the same asia Examples Asa result, the average particle diameter of nickel sulfide thus generated was 100 jm or more, which is too lange Compurative Example 4 ‘The sulfdization revetion was caused by setting the amount of nickel sulfide added as the seed erystal to 600% ‘by mass with respect othe amount of nike eontained inthe starting ighid and the blow quantity of hydrogen sulfide gas to be hlown into the first sulidization reaction tank to 0.37 [Now/kg-Ni. Incidentally, conditions other than these ae the same asia Examples,US 10,017,835 B2 15, As a result the nickel concentration in the fisal quid aller the sulfdization reaction was completed was 0.30 gL. Wwhici is significantly high and the aetual yield of nickel decreased. In addition, the average particle diameter of nickel sulfide thns obiined was 8 im, "As can he scen fom these results of Comparative Examples 1 to 4, it was found tha the particle diameter of nickel sulfide to be generated is minimized or maximized and the actual yield of nickel decreases under the conditions that the amount of nickel sulfide added as the seed crystal ‘exceeds the range of from 40 to 500% by mass aad the blow ‘quantity of hydrogen sulfide yas exceeds the range of fom. 030 t0 0:85 Nin g-Ni “The invention claimed is: 1. A method for producing nickel sulfide, the method ‘comprising oblaining nickel sulfide by blowing hydrogen sulfide gas into an acide solution of sulfuric acid contining nickel to cause a sllidization reaction, wherein nickel sulfide having a panicle diameter of from 10 t0 60 tm is recovered by swing a plarlity of sulfdizaion reaction tanks, adding nickel sulfide having a particle diameter of from $ 10-20 4m as a seed erystal to the acidic salution of sulfuric acid having a nickel concestration of from 0.5 to 5.0g/Linan amount to he ata proportion of from 40 to 500% by mass with respect to an amount of nickel contained in the acidic solution of sulfuric acid in first sulfidization reaction tank for initially causing @ sulidization reaction, and adjusting a blow quantity of hydrogen sulfide gas 10 be ‘lovin into the frst sulfdization reaction tank to fom 033 to 082 Nan'ke-Ni 2. The method for producing nickel sulfide acconding to ‘lai 1, wherein ‘ickel sulfide having a particle diameter of from 15 to 55 um is recovered by 16 adding nickel sulfide having a particle diameter of trom S 1 20 jm as the seed crystal ata proportion of from 100, to 150% by mass with respect to an amount of nickel ccontsined in the acidie solution of sulfuric acid con- laining nickel inthe frst sulidization reaction tank and adjusting a blow quantity of hydrogen sulfide gas to be blown into the fist sulfidization resetion tank to from (033 t0 082 Nav hke-Ni 3. The method for producing nickel sulfide according to claim 1, wherein nickel sulfide obtained by the sultiization waetion is repeatedly use as nickel sulfide to be added as the seed crystal 44. "The method for producing nickel sulfide according to claim 1, wherwin the acidic solution of sulfuric acid con- ‘aining nickel is « leachate obtained by subjecting nickel owkde ore fo 3 leaching treatment using sulfur acid in @ bbydrometallurgical method for nickel oxide ore. 5. 4 hyidrometaurgical method for nickel oxide ore 10 leach out nickel fom nickel oxide ore by using sulfur acid and to generate a sulfide containing nickel rom the leachate ‘oblained, The method comprising 4 sullization step of recovering nickel sulfide having a particle diameter of from 10 10 60 jm by using & plurality of sulidization reaetion tanks, adding nickel sulle having a particle diameter of from $ to 20 yum as ‘2 seed erystal to a leachate having a nickel concentra tion of from 0.5 to 5.0 gi. in an amount to be at a proportion of from 40 10 500% by mass with respect fn amount of nickel contains in the leachate i ist sullidization reaction tank for initially causing & sul= fidization reation, and adjusting a blow quantity of hydrogen sulfide gas t0 be ‘own into the frst sulfdization reaction tank 10 from (033 t0 0382 Nav kg-Ni